CN114276180B - Method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic bacteria residues - Google Patents
Method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic bacteria residues Download PDFInfo
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- CN114276180B CN114276180B CN202111599409.6A CN202111599409A CN114276180B CN 114276180 B CN114276180 B CN 114276180B CN 202111599409 A CN202111599409 A CN 202111599409A CN 114276180 B CN114276180 B CN 114276180B
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Abstract
The invention discloses a method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic fungi residues, which comprises the steps of grinding and mixing the forestry waste and the antibiotic fungi residues according to a mass ratio of 1: 1-10, and performing co-pyrolysis at 450-750 ℃ in an anaerobic environment to prepare the nitrogen-containing high-value chemicals, wherein the nitrogen-containing high-value chemicals comprise amides, nitrogen-containing heterocyclic compounds and nitriles. The forestry waste and the antibiotic bacteria residues are subjected to co-pyrolysis treatment, and the two have synergistic effect, so that the yield of the nitrogenous high-value chemical can be improved, and the harmless and resource treatment of the antibiotic bacteria residues of the dangerous chemicals and the resource utilization of the forestry waste can be realized.
Description
The technical field is as follows:
the invention relates to the technical field of comprehensive utilization of solid wastes, in particular to a method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry wastes and antibiotic fungi residues.
Background art:
at present, a large amount of fungus residues can be generated in the production process of antibiotics, and the annual output of the fungus residues can reach millions of tons according to the calculation of 8-10 tons of fungus residues generated in the production process of 1 ton of antibiotics. The main components of the antibiotic fungi residues comprise mycelium, intermediate metabolites, residual culture medium organic solvents, a small amount of residual antibiotics and the like. Because the organic matter content in the fungus dregs is higher, secondary fermentation can be caused, the color can become black, peculiar smell can be generated, and the environment is seriously influenced. In addition, once the antibiotics and resistance genes remaining in the antibiotic residues enter the environment, they are spread and enriched in the organism, which may eventually lead to the appearance and spread of pathogenic bacteria resistance, thereby causing the antibiotic drugs to lose the original therapeutic effect and finally endangering human health. The chemical components of the antibiotic residues are protein, amino acid and other substances, and the residues without the influence of residual medicines have high utilization value. There is an increasing interest in converting these nitrogenous materials into a wide variety of high-value chemicals by biological or chemical means. Meanwhile, billions of tons of wood processing residues, urban landscaping wastes and other forestry wastes are generated in China every year, and how to utilize the wastes as resources is widely concerned by researchers.
The invention content is as follows:
the invention aims to provide a method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic fungi residues.
The invention is realized by the following technical scheme:
a method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic fungi residues comprises the following steps: grinding and mixing forestry waste and antibiotic bacterium residues according to a mass ratio of 1: 1-10, and performing co-pyrolysis at 450-750 ℃ in an anaerobic environment to prepare a nitrogen-containing high-value chemical product, wherein the nitrogen-containing high-value chemical product comprises amide, a nitrogen-containing heterocyclic compound and nitrile.
The forestry waste is one of eucalyptus sawdust, eucalyptus bark and coconut shells with the particle size of 50-200 meshes.
The antibiotic bacterial residues are one of penicillin bacterial residues, tetracycline bacterial residues, terramycin bacterial residues and gentamicin bacterial residues with the particle size of 50-200 meshes.
The oxygen-free environment is nitrogen, argon or helium atmosphere.
The heating rate is 10-104℃/s。
Preferably, the holding time for the co-pyrolysis is 20 s.
The residual biochar material after pyrolysis can be further utilized as a fertilizer additive containing nitrogen and the like.
The invention utilizes the advantages of the chemical composition of the antibiotic mushroom dregs to make up the defect of low nitrogen content of forestry waste. In the biomass pyrolysis process, alkali metal and alkaline earth metal elements (AAEMs) can obviously change the distribution condition of pyrolysis products, and the agricultural and forestry waste contains more alkali metal and alkaline earth metal elements such as K, Ca and the like, so that the distribution condition of the pyrolysis products can be obviously changed. In addition, the main component of the agricultural and forestry waste is lignocellulose, and the main component can still keep a good pore structure after high-temperature pyrolysis carbonization, so that the release of pyrolysis volatile products is facilitated. In addition, lignin in the agricultural and forestry waste naturally contains abundant aromatic ring structures, and can promote the formation of high-value chemicals such as nitrogen heterocyclic compounds. Therefore, the method utilizes the physical and chemical characteristics of the agricultural and forestry waste and the antibiotic residues, adopts a pyrolysis mode to carry out cooperative treatment on the agricultural and forestry waste and the antibiotic residues, and realizes harmless and resource treatment of the hazardous waste antibiotic residues and resource utilization of the agricultural and forestry waste while preparing the nitrogen-containing high-value chemical.
The invention has the following beneficial effects:
1) according to the invention, the forestry waste and the antibiotic bacteria residues are subjected to co-pyrolysis treatment, and the co-pyrolysis treatment have synergistic effects, so that the yield of high-value nitrogenous chemicals can be improved, and the harmless and resource treatment of the antibiotic bacteria residues of dangerous chemicals and the resource utilization of agricultural and forestry waste can be realized.
2) After the forestry waste and the antibiotic fungi residues are pyrolyzed together, the residual biochar material can be further utilized as a nitrogenous fertilizer additive and the like.
3) The method is simple to operate, does not need to invest extra cost, and can be further popularized and applied to resource utilization of other nitrogenous wastes.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
uniformly grinding and mixing 100-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:2, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 104 ℃/s and under the condition that the pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 52.9 percent, wherein the relative content of amides is 5.4 percent, the relative content of nitrogen-containing heterocyclic compounds is 37.9 percent, and the relative content of nitriles is 9.6 percent. See table 1.
Example 2
Uniformly grinding and mixing 100-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:5, and performing co-pyrolysis at a pyrolysis temperature of 550 ℃, a temperature rise rate of 104 ℃/s and under the condition that the pyrolysis atmosphere is argon; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is 49.2 percent by calculation, wherein the relative content of amides is 3.3 percent, the relative content of nitrogen-containing heterocyclic compounds is 28.6 percent, and the relative content of nitriles is 17.3 percent.
Example 3
Uniformly grinding and mixing 100-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:10, and performing co-pyrolysis at a pyrolysis temperature of 750 ℃, a temperature rise rate of 104 ℃/s and under the condition that the pyrolysis atmosphere is helium; analyzing the relative content of various nitrogen-containing chemicals in the pyrolysis product by using a gas chromatography-mass spectrometer, and calculating to obtain the relative content of the nitrogen-containing compounds in the pyrolysis product to be 45.1%, wherein the relative content of amides is 0%, the relative content of nitrogen-containing heterocyclic compounds is 23.0%, and the relative content of nitriles is 22.1%.
Example 4
Uniformly grinding and mixing 200-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:1, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 104 ℃/s and in a pyrolysis atmosphere of nitrogen; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 50.8%, wherein the relative content of amides is 5.6%, the relative content of nitrogen-containing heterocyclic compounds is 38.4%, and the relative content of nitriles is 6.8%.
Example 5
Uniformly grinding and mixing 100-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:2, and performing co-pyrolysis at a pyrolysis temperature of 650 ℃, a temperature rise rate of 102 ℃/s and under the condition that the pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 47.4%, wherein the relative content of amides is 0.3%, the relative content of nitrogen-containing heterocyclic compounds is 24.4%, and the relative content of nitriles is 22.7%.
Example 6
Uniformly grinding and mixing 50-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:1.5, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 10 ℃/s and under the condition that a pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 53.4%, wherein the relative content of amides is 6.2%, the relative content of nitrogen-containing heterocyclic compounds is 36.0%, and the relative content of nitriles is 11.2%.
Example 7
Uniformly grinding and mixing 100-mesh eucalyptus sawdust and penicillin fungi residues in a mass ratio of 1:3, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 104 ℃/s and under the condition that the pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 50.2%, wherein the relative content of amides is 2.9%, the relative content of nitrogen-containing heterocyclic compounds is 40.3%, and the relative content of nitriles is 7.0%.
Example 8
Uniformly grinding and mixing 100-mesh eucalyptus sawdust and penicillin fungi residues according to the mass ratio of 1:1.2, and performing co-pyrolysis at the pyrolysis temperature of 550 ℃, the heating rate of 104 ℃/s and the pyrolysis atmosphere of argon; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 47.6%, wherein the relative content of amides is 1.4%, the relative content of nitrogen-containing heterocyclic compounds is 29.5%, and the relative content of nitriles is 16.7%.
Example 9
Uniformly grinding and mixing 200-mesh coconut shells and penicillin fungi residues in a mass ratio of 1:2, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a heating rate of 104 ℃/s and under the condition that the pyrolysis atmosphere is nitrogen; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is 49.7 percent by calculation, wherein the relative content of amides is 2.8 percent, the relative content of nitrogen-containing heterocyclic compounds is 40.1 percent, and the relative content of nitriles is 6.8 percent.
Example 10
Uniformly grinding and mixing 100-mesh eucalyptus bark and penicillin fungi residues in a mass ratio of 1:1, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 10 ℃/s and under the condition that the pyrolysis atmosphere is argon; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 52.5%, wherein the relative content of amides is 4.4%, the relative content of nitrogen-containing heterocyclic compounds is 38.2%, and the relative content of nitriles is 9.9%.
Example 11
Uniformly grinding and mixing 100-mesh eucalyptus bark and tetracycline bacteria residue in a mass ratio of 1:2, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 104 ℃/s and under the condition that a pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 52.1 percent, wherein the relative content of amides is 4.8 percent, the relative content of nitrogen-containing heterocyclic compounds is 38.2 percent, and the relative content of nitriles is 9.1 percent.
Example 12
Uniformly grinding and mixing 200-mesh coconut shells and terramycin mushroom residues according to the mass ratio of 1:2, and performing co-pyrolysis under the conditions that the pyrolysis temperature is 450 ℃, the heating rate is 104 ℃/s and the pyrolysis atmosphere is nitrogen; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is 49.9 percent by calculation, wherein the relative content of amides is 2.4 percent, the relative content of nitrogen-containing heterocyclic compounds is 39.6 percent, and the relative content of nitriles is 7.9 percent.
Example 13
Uniformly grinding and mixing 50-mesh eucalyptus bark and gentamicin mushroom dregs in a mass ratio of 1:1.5, and performing co-pyrolysis at a pyrolysis temperature of 450 ℃, a temperature rise rate of 10 ℃/s and under the condition that a pyrolysis atmosphere is helium; the relative content of various nitrogen-containing chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the nitrogen-containing compounds in the pyrolysis product is calculated to be 50.5%, wherein the relative content of amides is 5.8%, the relative content of nitrogen-containing heterocyclic compounds is 34.1%, and the relative content of nitriles is 10.6%.
TABLE 1
Claims (4)
1. A method for preparing nitrogen-containing high-value chemicals by co-pyrolysis of forestry waste and antibiotic fungi residues is characterized by comprising the following steps: grinding and mixing forestry waste and antibiotic fungi residues according to a mass ratio of 1: 1-10, performing co-pyrolysis at 450-750 ℃ in an anaerobic environment, wherein the heating rate is 10-104Performing co-pyrolysis at the temperature of 10-60 s to obtain a nitrogen-containing high-value chemical product, wherein the nitrogen-containing high-value chemical product comprisesIncluding amides, nitrogen-containing heterocycles, and nitriles; the forestry waste is one of eucalyptus sawdust, eucalyptus bark and coconut shells with the particle size of 50-200 meshes; the antibiotic bacterial residues are one of penicillin bacterial residues, tetracycline bacterial residues, terramycin bacterial residues and gentamicin bacterial residues with the particle size of 50-200 meshes.
2. The method of claim 1, wherein the oxygen-free environment is a nitrogen, argon or helium atmosphere.
3. The method of claim 1, wherein the co-pyrolysis is carried out for a holding time of 20 seconds.
4. The method according to claim 1, characterized in that the biochar material remaining after pyrolysis is further utilized as a fertilizer additive containing nitrogen.
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Citations (4)
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| GB9424914D0 (en) * | 1994-12-09 | 1995-02-08 | Radlein Desmond S G | Method of producing slow-release nitrogenous organic fertilizer frpm biomass |
| CN105110826A (en) * | 2015-09-15 | 2015-12-02 | 北京观澜科技有限公司 | Microbial fertilizer manufacturing method, prepared microbial fertilizer and compound microorganism preparation |
| CN107099314A (en) * | 2017-06-27 | 2017-08-29 | 华中科技大学 | A kind of utilization agriculture and forestry organic waste material prepares long chain fatty acids and the method for nitrating carbon |
| CN110256115A (en) * | 2019-06-20 | 2019-09-20 | 吴植仁 | A kind of antibiotic bacterium dregs and farm's animal wastes recycling treatment system |
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- 2021-12-24 CN CN202111599409.6A patent/CN114276180B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9424914D0 (en) * | 1994-12-09 | 1995-02-08 | Radlein Desmond S G | Method of producing slow-release nitrogenous organic fertilizer frpm biomass |
| CN105110826A (en) * | 2015-09-15 | 2015-12-02 | 北京观澜科技有限公司 | Microbial fertilizer manufacturing method, prepared microbial fertilizer and compound microorganism preparation |
| CN107099314A (en) * | 2017-06-27 | 2017-08-29 | 华中科技大学 | A kind of utilization agriculture and forestry organic waste material prepares long chain fatty acids and the method for nitrating carbon |
| CN110256115A (en) * | 2019-06-20 | 2019-09-20 | 吴植仁 | A kind of antibiotic bacterium dregs and farm's animal wastes recycling treatment system |
Non-Patent Citations (2)
| Title |
|---|
| Yifei Li等.Nitrogen Migration Mechanism during Pyrolysis of Penicillin Fermentation Residue Based on Product Characteristics and Quantum Chemical Analysis.《 ACS SUSTAINABLE CHEMISTRY & ENGINEERING》.2020,第8卷(第20期),第7721-7740页. * |
| 司艳晓等.热解温度对青霉素菌渣热解产物的影响.《化工环保》.2021,第41卷(第2期),第190-195页. * |
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